ABSTRACT
Next-generation electrochemical energy storage materials are essential in delivering high power for long periods of time. Double-layer carbonaceous materials provide high power density with low energy density due to surface-controlled adsorption. This limitation can be overcome by developing a low-cost, more abundant material that delivers high energy and power density. Herein, we develop layered C3N4 as a sustainable charge storage material for supercapacitor applications. It was thermally polymerized using urea and then protonated with various acids to enhance its charge storage contribution by activating more reaction sites through the exfoliation of the C-N framework. The increased electron-rich nitrogen moieties in the C-N framework material lead to better electrolytic ion impregnation into the electrode, resulting in a 7-fold increase in charge storage compared to the pristine material and other acids. It was found that C3N4 treated with hydrochloric acid showed a very high capacitance of 761 F g-1 at a current density of 20 A g-1 and maintained 100% cyclic retention over 10,000 cycles in a three-electrode configuration, outperforming both the pristine material and other acids. A symmetric device was fabricated using a KOH/LiI gel-based electrolyte, exhibiting a maximum specific capacitance of 175 F g-1 at a current density of 1 A g-1. Additionally, the device showed remarkable power and energy density, reaching 600 W kg-1 and 35 Wh kg-1, with an exceptional cyclic stability of 60% even after 5000 cycles. This study provides an archetype to understand the underlying mechanism of acid protonation and paves the way to a metal-carbon-free environment.
ABSTRACT
Amorphous copper oxide (Cu(II)) nanoclusters function as efficient electrocatalysts for the reduction of carbon dioxide (CO2) to carbon monoxide (CO). In addition to promoting electrocatalytic activity, Cu(II) nanoclusters act as efficient cocatalyts for CO2 photoreduction when grafted onto the surface of a semiconductor (light harvester), such as niobate (Nb3O8(-)) nanosheets. Here, the photocatalytic activity and reaction pathway of Cu(II)-grafted Nb3O8(-) nanosheets was investigated using electron spin resonance (ESR) analysis and isotope-labeled molecules (H2(18)O and (13)CO2). The results of the labeling experiments demonstrated that under UV irradiation, electrons are extracted from water to produce oxygen ((18)O2) and then reduce CO2 to produce (13)CO. ESR analysis confirmed that excited holes in the valence band of Nb3O8(-) nanosheets react with water, and that excited electrons in the conduction band of Nb3O8(-) nanosheets are injected into the Cu(II) nanoclusters through the interface and are involved in the reduction of CO2 into CO. The Cu(II) nanocluster-grafted Nb3O8(-) nanosheets are composed of nontoxic and abundant elements and can be facilely synthesized by a wet chemical method. The nanocluster grafting technique described here can be applied for the surface activation of various semiconductor light harvesters, such as metal oxide and/or metal chalcogenides, and is expected to aid in the development of efficient CO2 photoreduction systems.
